Understanding the Highly Varying pKa of Arylamines. A Perspective from the Average Local Ionization Condensed-to-Atom Framework

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)

Original languageEnglish
Pages (from-to)8156-8162
Number of pages7
JournalJournal of Physical Chemistry A
Volume119
Issue number29
DOIs
Publication statusPublished - 23 Jul 2015

Fingerprint

Ionization
Ionization potential
Alkalinity
ionization
Atoms
nitrogen atoms
atoms
reactivity
valence
orbitals
energy
evaluation
Nitrogen

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{4147f6c5c770460da004ebfce0c2021f,
title = "Understanding the Highly Varying pKa of Arylamines. A Perspective from the Average Local Ionization Condensed-to-Atom Framework",
abstract = "The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)",
author = "Eduardo Chamorro and Mario Duque-Nore{\~n}a",
year = "2015",
month = "7",
day = "23",
doi = "10.1021/acs.jpca.5b03252",
language = "English",
volume = "119",
pages = "8156--8162",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "29",

}

TY - JOUR

T1 - Understanding the Highly Varying pKa of Arylamines. A Perspective from the Average Local Ionization Condensed-to-Atom Framework

AU - Chamorro, Eduardo

AU - Duque-Noreña, Mario

PY - 2015/7/23

Y1 - 2015/7/23

N2 - The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)

AB - The highly varying experimental pKa values for 36 arylamines spanning 7 orders of magnitude is carefully examined. Within this framework, a valence condensed-to-atom model for the average ionization energy is introduced and tested. The theoretical approach is connected to orbital Fukui functions directly mapped into semilocal or regional site-specific responses. It is revealed that the average local ionization energies associated with the amino nitrogen atom is linearly correlated to the basicity of the substituted arylamines, properly reproducing the experimental ordering of basicity. The condensed-to-atom descriptor exhibits a high predictive power, providing a new direct reactivity evaluation of significant value. (Graph Presented)

UR - http://www.scopus.com/inward/record.url?scp=84937955463&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.5b03252

DO - 10.1021/acs.jpca.5b03252

M3 - Article

AN - SCOPUS:84937955463

VL - 119

SP - 8156

EP - 8162

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 29

ER -